Hydrogenolysis process utilizing suspended catalyst



Aug- 16, 1955 w. c. I ANNING ET AL HYDROGENOLYSIS PROCESS UTILIZING SUSPENDED CATALYST Filed Sept. 30, 1952 United States Patent Of ice HYDROGENGLYSIS PRCESS UTILIZIDIG SUSPENDED CATALYST Wiiliam C. Lann-.ing and Reagan T. Wilson, Bartlesville, Okla., assignors to Phillips Petroeum Company, a cor poration of Delaware Appiication September 30, 1952, Serial No. 312,262

l1 Ciaims. (Cl. 196-53) This invention relates to the destructive hydrogenation or hydrogenolysis of heavy oils. ln one aspect it relates to an inmproved process for the hydrogenolysis of heavy oils utilizing a suspended catalyst. ln another aspect it relates to the removal of asphaltenes and other heavy carbonaceous material from a recycle stream in such a process.

The hydrogenolysis of heavy oils in the presence of a catalyst has been used for a number of years to convert heavy oils having limited utility to lighter oils having greater utility. lt is known to conduct such a process in the presence of a fixed-bed catalyst. lt is also known to use a iinelyfdivided or suspended catalyst in such a process. The use of a suspended catalyst has the advantage that milder reaction conditions can be utilized and higher through-puts can be attained.

One difculty accompanying the use of a suspended i tion zone in which a gaseous phase is separated from a liquid phase; the liquid phase is Withdrawn from the separation zone and a predominantly paraiijnic hydrocarbon is added to said liquid phase to precipitate asphaltenes and other heavy carbonaceous material; the liquid material is then filtered to remove the precipitated carbonaceous material together lwith theV s118- pended catalyst and a clean filtrate substantially free from heavy carbonaceous materials is obtained for recycle to the reactor.

It is known in the hydrogenolysis art to withdraw from the hydrogenolysis reactor the total product and to separate the gaseous phase from the liquid phase of said product in a conventional gas-liquid separator or catch-pot at substantially the temperature of the hydrogenolysis reactor. Such practice is utilizable in connection with this invention, However, it has been found, in the hydrogenolysis of many heavy oils, that the liquid phase so obtained has a marked tendency to solidify upon cooling and it is therefore necessary in many cases to heat the liquid phase in order to maintain it in a liquid and transferable condition. The settling of asphaltenes from the liquid phase so obtained is difficult because at the temperatures at which Said phase is uent, the asphaltenes are also fluent and do not settle readily, and at lower temperatures at which asphaltenes are less fluent and would be more readily separatable, in part, by settling, the total material solidiiies or assumes a non-fluent state.

Further in accordance with this invention, the foregoing problem is solved by cooling the total hydro- P genolysis efliuent prior to the gas-liquid separation. The total eiluent is cooled to a temperature in the range intentada Aug. l5, ldt? 80 F. to 200 F., preferably 100 F. to 130 F.. lt has been found that when such cooling is practiced, prior to settling, in accordance with this invention a liquid phase is obtained which remains normally liquid at ambient temperatures and requires no heating for transfer, and a preliminary settling of asphaltenes from the liquid phase can be effected, as subsequently described.

Further in accordance with this invention, the liquid phase of the hydrogenolysis product can be subjected to settling to obtain a solid-liquid slurry containing substantially all of the suspended catalyst. In this preliminary settling step, some of the asphaltenes adhere to the catalyst and to any coke present and are carried down with the settled catalyst and coke, thus effecting a preliminary precipitation and concentration of asphaltenes. The slurry is then treated by the addition of a normal paraiiinic hydrocarbon to further precipitate asphaltenes and other carbonaceous material prior to filtration. In this mode of operation, the amount of hydrocarbon added is substantially reduced and an advantageous preliminary precipitation and concentration of asphaltenes in the settled slurry is effected. Furthermore, the precipitated asphaltenes, being admixed with coke and catalyst, are more readily settled than they would be in the absence of coke and catalyst.

ln accordance with a further embodiment of the invention, the settled slurry obtained as previously described can be subjected to distillation to remove lowboiling materials prior to addition of the parainic hydrocarbon. The materials removed by distillation are ordinarily those boiling below 850 F. and preferably those boiling below 1100 F. This mode of operation can be practiced either with or without the settling step previously described.

The paraliinic hydrocarbon added to the liquid phase in accordance with this invention is preferably a paraflinic hydrocarbon having from 4 to 9 carbon atoms per molecule. Examples of such hydrocarbons are parafiinic naphthas, normal heptane, normal pentane, normal butane, normal hexane and normal octane. The amount of paraiinic hydrocarbonv added is in the range 0.5 to 2 volumes per volume of liquid oil treated. The temperature of precipitation of the asphaltenes and other heavy carbonaceous material from the liquid phase product is in the range 40 F. to 310 F. and preferably in the range 70 F. to 210 F. The pressure used for the precipitation step is preferably sucient pressure to maintain the mixture substantially in the liquid phase, including the added parainic hydrocarbon.

The oils subjected to hydrogenolysis in accordance with this invention are oils having an initial boiling point about 400 F. and more frequently are heavier oiis having an initial boiling point above 700 F. ln many cases, oils having an initial boiling point of at least 850 F. are used as starting materials and oils having an initial boiling point of 1100 F. and higher are also frequently used.

The catalyst used in the hydrogenolysis step can be any finely-divided catalyst known in the hydrogenolysis art. Examples of such catalysts are molybdena, iron or iron oxides, molybdenum sulde, tin sulfide, and vanadia. Preferably the catalysts are supported on a porous support or other material having a relatively high surface area per unit weight. Examples of such supports are porous charcoal, carbon black, alumina, and silica-alumina.

The temperature of hydrogenolysis is in the range 800 F. to 950 F., preferably 850 F. to 925 F. The pressure is inthe range 1000 to 10,000 p. s. i., preferably 3,000 to 6,000 p. s. i. The liquid charge rate is in the range 0.1 to 5 volumes of oil per Volume of reactor space per :value near that of Vthe hydrogenolysis temperature.

Ythrough conduit 12.

hour, preferably 0.5 to 2 volumes` per volume perhour. The'hydrogen flow rate is ordinarily in the range 500 to `20,000, preferably 5,000 to 10,000, cubic feet per barrel of oil. The amount of catalyst used is in the range 0.1 Vto weight per cent, preferably l to 4 weight per cent, based on the weight of the oil.

' cled'oil and catalyst are added through conduit 9. The

heated charge passes through conduit 4 to hydrogenolysis Zone 5 in which the mixture is subjected to hydrogenolysis conditions previously described.

AThe total effluent from hydrogenolysis zone 5 passes through conduit 6 to gas-liquid separation zone 7. The gas and vapor phase from the separation zone passes through conduit'18 and cooler 19 to separator 20. Normally gaseous material is removed from separatorY through conduit'r28 and, since it contains a large proportion of hydrogen, it is recycled through conduit 25. Any unneeded excess of this gas can be removed through vent `line 27. The liquid material from separation zone 2t) is passed Ythrough conduit 21 to product separation zone 22 from which product'fractions are removed through conduits 23 and 24. These product fractions are ordinarily gasoline and gas oil,rwhich can be used as a catalytic cracking stock. Other fractions can, of course, be recovered Vas desired.

The liquid phase containing suspended catalyst is with- .Y drawn from separation Yzonet7 through conduit 8. Part offthis material can be recycled through conduit 9. Ac-

cording to this invention part of the liquid material is. passedrthrough conduit 10. A parainic hydrocarbon material,'such as normal heptane,ris mixed with this Y. liquid material, Athe paralnic hydrocarbon entering through yinlet 11 and conduit 12. The mixture so obtained is passed to lter zone 13 in which suspended cataalyst and precipitated asphaltenes and other carbonaceous, Y material are removed through conduit 14.V This material may be discarded or treated for recovery of the catalytic constituents as economic principles require.

The filtrate from filter zone 13 is passed through conz' duit 15 to separation zone 16 in which the added paraffnic hydrocarbon is recovered by distillation and'recycled The recovered and purified recycle oilis recycled to hydrogenolysis zone 5 through conduits Another embodiment of the invention is illustrated dia- Y grammatically in Figure 2.

Oil and catalyst enter hydrogenolysis zone 32 through lines and 30A. Hydrogen is added through line 31 v and recycle material through line 56. The hydrogenolysis eluent'passes through cooler 33 and line 34 and the euent cooled in accordance with this invention, is passed tion of carbonaceous materials in the recycle stocks is notVY It isevident from the last column in this't'ableV 4 Y to gas-liquid separation zone 35. Gaseous material is recycled through conduit 41, as previously described, excess gas being vented through outlet 42. n Y

In separation zone 35 a normally liquid material is obtained as the liquid phase. passed through conduit 36 to settling zone 37, wherein suspended catalyst, together withcoke and some of the asphaltenes are caused to settle out of the liquid. The settled slurry, containing catalyst, coke, asphaltenes, and some of the liquid oil, is withdrawn from the bottom of settling zone 37 and passed through conduit 43 to distillation zone 45. Clarified liquid ,is withdrawn Vfrom zone 37 through conduit 38 and passed to product distillation, zone 39, distillate products being recovered through outlet 40 and heavier materials being recycled through line'56.

If desired, part or all of the liquid phase can be bypassed around settling zone 37 through conduit 44,

In distillation zone the slurry is subjected toY distillafrom Yfilter zone are removed through Aoutlet 52. This solid material includes catalyst, asphaltenes and other pref, The filtrate is passed cipitated 'carbonaceous material. through conduitSl to distillation zone 53 wherein the added paranic hydrocarbon is recoveredV by distillationk and recycled through line 49. TheV purified oil obtained as a residue of distillation zone 53V can be recycled through i lines 55 and 56. Part of the recovered oil can be passed through line 54 to distillation zone 39 if desired, particularly whenit is desired not to utilize distillation zone 45V Y but to by-pass it by means now shown. Y Y

The embodiment shown in ,Figure 2 has two advantages, namely, (1) a normally `liquid material is always obtained in liquid-gas separator 35, and (2) the amount of added parahnic hydrocarbon used to precipitate as-V phaltenes, and also the filtration `capacity required, are reduced. Y

EXAMPLE IV The following table shows data obtainable Yin, a sus- Vpended catalyst hydrogenolysis process wherein' precipitapracticed. thatthe product residue boiling vabove 850 F. contains large amounts of carbonaceous material, as evidencedby the Ramsbottom carbon'residue. Y Y Y.

The charge material in this process was a distillation residue obtained in a commercialV refinery. The hydrogenolysis was conducted at a total pressure of 4,000 p. s. i., a temperature of 875 F., a liquid vcharge rate fof 2 volumes per volume of reactor space Vper hour, and a hydrogen ow rate of 10,000l cubic feet per barrel of oil.

Catalytic hydrogenolyss of refinery distillation residue C Catalyst 850 F.+Residue on- Rml Product, version Hours No AP I ol., On Wt Wt Pep Support VYield f Rams- Gravity Per- Stream Y ol. Gravity, bottom Percent cent Procent) of Chg moter Per- API Carbon cent) Residue 80. 5 21. 9 6. 15. 6 16. 2 5. 14. 2 13. 2 Y 14. 19. 3 14. 7 12. do 10. 4 13. 2 14. Y Pelleted Carbon 11.0 9.3 18.

Y Black. 36. 4 88. 1 do Y 9. 2 8. 8 18.

This liquid'material is Y y treatment of the recycle material according to this invention the carbonaceous materials in the recycle stream can be reduced, as shown in the subsequent examples.

EXAMPLE II distillation residue in the ratio of lO ml. to -l j gram ofthe oil. The data in the following table show the amountsof materials of the types of asphaltenes removed byprecipitation with the normal heptane` The precipitation hwas conducted at approximately the boiling point of normal heptane at atmospheric pressure.

Fuel Oil .liesiduum Charge D t s l'd D t soi'd 803D 01 S 803D. I S" ou 011 Charge on on Cllafvge 850 F.+product,

wt. percent of A charge 36.1 A135 87.4 43.1 6.3 100 Asphaltenes:l A

Wt. percent of produ@c.;; "3.2 4 43.2 4.8 36.6 Wt. percent of A charge 3.0 5.8 2.1 2.3

Total, wt. per- Y cent of charge. 8. 8 8.8 9. 9 4. 4 4; 4 .07

l Iusoluble in n-heptaue.

The above data show that deleterious carbonaceous or asphaltic materials are effectively removed'from the'hy'fV drogenolysis products by precipitation with normal heptane according to this invention.

EXAMPLE in v In a hydrogenolysis system of the type illustrated in Figure 2, a residuum oil having an initial boiling point of about 1100o F. is subjected to hydrogenolysis'. A conversion of 80% is obtained per pass. 'The products are materials boiling from the boiling point of pentanesY to 1100n F. The amount of catalyst used is 1% by weight of the charge, converted.V The ow system issubstaritially the same as that in Figure 2 except for the fact that a centrifuge is used in place of settling zone 37. The material withdrawn from the centrifuge through line 43 contains 30 weight per cent total solids, including asphaltenes. In distillation zone 45, materials boiling below ll00 F. are removed from the slurry. The amount of normal heptane added through line 49 is five volumes per volume of slurry. The following table shows the relative weight proportions of the materials in the several conduits, based on 100 parts by weight of the residuum charge. The numerals at the head of each column in the following table correspond to the reference numerals in Figure 2 indicating the conduits in the system.

'6 to distillation zone 4S, 'which is operated as described4v in Example' III.- The following table shows the data obtained which correspond to the data in the table in Example III.

Stream Proportions, Parts by Weight conduit... 30 30.4 uf 46 52 56 .m

Distillate 1100 F. -I- oil. 100 125 Catalyst Asphalten Plfhe data in Examples III and lV show that asphaltenes arev eiectively removed according to the process of this invention and further that the elimination of a settling or centrifuging zone results in an increased amount of residual oil which has to be treated for the removal of catalyst, asphaltenes and other carbonaceous materials. Thus, the Yvolume of residual oil treated according to Example III was only about one-eighth of that treated according to Example IV and much larger quantities of parafiinic hydrocarbon and larger filtration capacity were required in Example IV.

"Theamount of asphaltenes and other carbonaceous impurities removed from the recycle oil can be varied hydrocarbon within thel disclosed limits.

` lt is evident from the foregoing disclosure that catalyst concentrations in the hydrogenolysis zone can be increased or decreased as desired by varying the proportions of 'catalyst returned to the vreactor in suspension in the 35 recycled oil.

Variation and modification are possible within the scope oftheforegoing disclosure and the claims to this invention, the essence of which is that a suspended catalyst 'type hydrogenolysis process can be operated and the 59 undesired accumulation of heavy carbonaceous materials in the recycle stream can be minimized by separating a total" reactor efuent into a gas phase and a liquid phase, adding to said liquid phase a paraiiinic hydrocarbon having from 4 yto 9 carbon atoms per molecule, ltering the mixture so obtained and returning the filtrate to the hydrogenolysis reactor after recovery of the added paraflinic hydrocarbon; that further improvement in the process is obtained by cooling the total hydrogenolysis product prior to'the Ygas-liquid separation; that still further improvement is obtainable by subjecting the liquid phase to settling or centrifuging prior to treatment with the parafinic hydrocarbon; and that still further improvement is obtained by distilling materials boiling below 850 F. from the liquid phase prior to addition of said 55 parafnic hydrocarbon. Methods other than filtration, e. g. centrifuging or decanting, can be used to remove catalyst and precipitated carbonaceous impurities from the parain-treated recycle oil.

We claim:

C() 1 In a process in which a hydrocarbon oil having an initial boiling point higher than 400 F. is subjected to Stream Proportions, Parts by Weight Conduit 30 30.4 36 38 43 46 52 55 56 Distillates 94 8l. 2 12. 2 0 25 21.3 3.2 0

EXAMPLE IV hydrogenolysis in the presence of a suspended hydro- In a system of the type shown in Figure 2, centrifuge or settling zone 37 is omitted, the liquid phase from separation zone 35 being passed through conduits 36 and 44 genolysis catalyst, the improvement which comprises the following steps in combination: subjecting a total hydrogenolysis product to gas-liquid separation to produce as' desired'by varying the proportions of added parainic Y step.

f 2. In a processrin which a hydrocarbon oil having an initial boiling point of at least 850 F.-is subjected to hydrogenolysis in the presence of a suspended hydrogenolysis catalyst, the improvement comprising Athe following steps in combination: cooling the total eluent from the hydrogenolysis step to a temperature in the range'y 80 F. to 200 F., subjecting the cooled eiuent to gas-liquid separation to obtain a gaseous Vphase and a Y Vliquid phase, adding to said liquid phase-.from 0.5 to 2 volumes of a predominantly parainic hydrocarbon containing from 4 to 9 carbon atoms per irfolecule, filtering themixture so robtained to recover a liq'tid hydrocarbon mixture 'substantially free from asphalt'enes and other heavy carbonaceous impurities, recovering said parafiinic hydrocarbon from said oil and recycling a fraction of said oil boiling above 850 F. to the hydrogenolyss step.

3. ln a process in which a hydrocarbon oil having an initialboiling pointof'at least 850 is subjected to hydrogenolysis in the presence ,of a suspended hydro-V n genolysis catalyst, the improvement which comprises the following stepsY in combination: subjecting the total hydrogenolysis' eluent to cooling to a temperature in the range Y100" F. to 130 F.,'subjecting the cooled eilluent to gas-liquid separation to obtain a gaseous phase and a liquid phase, subjecting said liquid phase to separation conditions to obtain a solid-free oil andva slurry, adding to said slurry from 0.5 to 2 volumes of la predominantly parainic hydrocarbon having from y4 to 9 carbon atoms per molecule, filtering said slurry to obtain a ltrate oil substantially free'from carbonaceous impurities, recoverv ing said parainic hydrocarbon from said rltrate oil, and Vrecycling a fraction of said filtrate oil boiling above 850 i F. to the hydrogenolysis step.

4. The process of claim 3 in which said predominantly Y l parainic hydrocarbon is a parainic naphtha.

7. The process of claim 3 in which said predominantly parafnic hydrocarbon is normal heptane. Y

8. The process of claim 3 in which said predominantly parainic hydrocarbon is normal octane.

9. The process of claim 3 in which said slurry is sub-V jected to distillation to removel materials boiling below 1100 F. prior to addition of said predominantly paranic hydrocarbon.

l0. The process of claim 3 in which said slurry is subjected to distillation to remove Vmaterials boiling below 850 F. prior to addition of said predominantly paranic hydrocarbon. 3

' 11. In a hydrogenolysis process inV which a hydrocarbon oil having an initial boiling point of at least 850 F. is subjected to hydrogenolysis in the presence of a sus-Y pended hydrogenolysis catalyst at a temperature in the range 800 F. to 950 F., a total pressure in the range 1,000 to 10,000V p. s. i., a liquid space velocity of 0.1 to 5 volumes of said oil per volume of reactor space per hour,

and a hydrogen flow rate in the range -500 to 20,000 cubic feet of hydrogen per barrel of oil, the amount of catalyst suspended in said oil being in the range 0.1 to 5 weight.

perY cent of said oil, the improvement which comprises the following steps in combination: cooling the total hydrogenolysis eluent to a temperature in the range 80 F. to 200 F.; subjecting the cooled eiuent to gas-liquid s'eparation to obtain a liquid phase and a gaseous'phase; subjecting said liquid phase to settling to obtain a solid-free oil and a slurry; recovering said solid-free oil as a product of the process; subjecting said: slurry to distillation to remove materials boiling below 1100 F.; recycling part` of the distillation residue to the hydrogenolysis step; adding to the remainder of the residue from said distillation from 0.5 to 2 volumes of normal heptane per volume of said slurry; maintaining said slurry at a temperature in the range F. to the boiling point of normal heptane,

whereby heavy carbonaceous impurities are precipitated; filtering Vthe mixture to obtain a hydrocarbon mixture substantially free of heavy carbonaceous impurities; recovering normal heptane from said mixture; and recycling the:Y normal heptane-free material so obtained to the hydrogenolysis step. A

References Cited in the le of this patent UNITED STATES PATENTS 2,447,149 Wier Aug. 17, 1948 2,502,958 Johnson Apr. 4, 19750 2,559,285 Douce July 3, 1951 

1. IN A PROCESS IN WHICH A HYDROCARBON OIL HAVING AN INITIAL BOILING POINT HIGHER THAN 400* F. IS SUBJECTED TO HYDROGENOLYSIS IN THE PRESENCE OF A SUSPENDED HYDROGENOLYSIS CATALYST, THE IMPROVEMENT WHICH COMPRISES THE FOLLOWING STEPS IN COMBINATION: SUBJECTING A TOTAL HYDROGENOLYSIS PRODUCT TO GAS-LIQUID SEPARATION TO PRODUCE A GASEOUS PHASE AND A LIQUID PHASE CONTAINING A SUSPENDED CATALYST, ADDING TO SAID LIQUID PHASE FROM 0.5 TO 2 VOLUMES PER VOLUME OF SAID LIQUID PHASE OF A PREDOMINANTLY PARAFFINIC HYDROCARBON HAVING FROM 4 TO 9 CARBON ATOMS PER MOLECULE, THEREBY PRECIPITATING ASPHALTENES AND OTHER CARBONACEOUS IMPURITIES, REMOVING SOLIDS FROM THE SYSTEM, RECOVERING A SOLID-FREE OIL AND RECYCLING A HEAVY FRACTION OF SAID OIL, FREE OF PRECIPITATED ASPHALTENES AND CARBONACEOUS IMPURITIES, TO THE HYDROGENOLYSIS STEP. 